Derivative of glucose and of vitamin F, compositions comprising it, uses and preparation process

ABSTRACT

An O-acyl product derived from glucose which may be obtained by partial or total esterification of glucose and of vitamin F, comprising a mixture of esters, for example, monoesters, of glucose and of at least one acid chosen from linoleic acid, oleic acid, palmitic acid and stearic acid, compositions, for example, cosmetic and pharmaceutical compositions, comprising this novel derivative, and their use for improving the condition of head hair and/or other hairs, and, for example, for reducing and/or impeding the loss of head hair and/or other hairs, and/or for inducing and/or stimulating hair growth, as well as a process for preparing O-acyl derivatives mainly in position 6 of glucose, comprising preparing a mixed anhydride by reacting a carboxylic acid with a trimethylacetyl halide, followed by reacting said mixed anhydride formed with glucose.

This is a continuation of application Ser. No. 10/459,539, filed Jun.12, 2003, and claims the benefit of U.S. Provisional Application No.60/390,440, filed Jun. 24, 2002, and the benefit of U.S. ProvisionalApplication No. 60/390,445, filed Jun. 24, 2002, all of which areincorporated herein by reference.

Disclosed herein are novel O-acyl derivatives of glucose, their use, forexample, in cosmetics or in pharmaceuticals, for example, for combatinghair loss, and compositions, for example, cosmetic or pharmaceuticalcompositions, comprising at least one of these derivatives. Furtherdisclosed herein is a novel process for preparing the glucosederivatives, said derivatives being O-acylated mainly in position 6 ofthe glucose.

In human beings, hair growth and its renewal can mainly be determined bythe activity of the hair follicles and their dermo-epidermalenvironment. Their activity can be cyclic and essentially can comprisethree phases, namely the anagenic phase, the catagenic phase and thetelogenic phase.

The active anagenic phase or growth phase, which can last several yearsand in the course of which the hair gets longer, is followed by a veryshort and transient catagenic phase which can last a few weeks, and thenby a rest phase, known as the telogenic phase, which can last a fewmonths.

At the end of the rest period, the hairs fall out and a new cyclestarts. The hair is thus in constant renewal and, out of theapproximately 150,000 hairs which make up a head of hair, at any moment,about 10% of them are at rest and will thus be replaced within a fewmonths.

In a large number of cases, early loss of hair can occur in individualswho are genetically predisposed, and this, for example, can affect men.This, for example, involves androgenetic or androgenic alopecia orandrogeno-genetic alopecia.

This alopecia can essentially be due to a disruption in hair renewal,which can result, in a first stage, in acceleration of the frequency ofthe cycles at the expense of the quality and then the quantity of thehairs. A gradual thinning of the head of hair can take place byregression of the so-called “terminal” hairs at the downy stage. Certainregions can preferentially be affected, for example, the temporal orfrontal areas and the upper part of the occipital bone in men, and adiffuse alopecia of the vertex can be observed in women.

Substances for suppressing or reducing the effect of alopecia, forexample, for reducing or slowing down hair loss or for inducing orstimulating the growth of head hairs and/or other hairs, have beensought for many years, for example, in the cosmetics industry.

In this respect, a large number of very diverse active compounds hasalready been proposed, such as 2,4-diamino-6-piperidinopyrimidine3-oxide, or “Minoxidil”, and also the many derivatives thereof.

Oligosaccharides containing at least one disaccharide unit comprising auronic acid residue and a hexosamine residue have also been proposed,for example, in EP 211 610.

Patent application WO-A-93/02657 teaches that compounds ofalkylpolyglycoside type and/or O-acyl derivatives of glucose may make itpossible to induce and stimulate hair growth and to reduce hair losseffectively. This patent application WO-A-93/02657, for example,describes the use of derivatives corresponding to the formula:

wherein R is chosen from saturated and unsaturated, linearhydrocarbon-based chains comprising from 7 to 19 carbon atoms,for combating hair loss or for stimulating hair growth, for example, incosmetics or pharmaceuticals.

This document WO-A-93/02657 mentions, inter alia, the use of derivativeswherein the acyl residue RCO— is chosen from octanoyl, decanoyl,dodecanoyl, myristoyl, hexadecanoyl, stearoyl, oleoyl, linoleoyl andlinolenoyl residues.

For example, the radicals mentioned and given as examples are theoctanoyl and oleoyl radicals.

It remains, in general, that it would be advantageous and useful to haveavailable active compounds other than those already known, which can bepotentially more active and/or less toxic, and which may be used in thecosmetics field.

After extensive research, the inventors have now demonstrated that,surprisingly and unexpectedly, a certain novel product, an O-acylderivative of glucose, has at least one of the following noteworthyproperties capable of justifying its use for improving the condition ofthe hair: reducing the loss of head hair and/or other hairs, impedingthe loss of head hair and/or other hairs, inducing hair growth, andstimulating hair growth.

For example, the product disclosed herein can have the advantage ofbeing composed mainly of essential fatty acid derivatives naturallypresent in the human body.

This product can also be more stable over time than the free fatty acidsit comprises.

Finally, it can be easy to synthesize at an industrial level, and can besynthesized relatively inexpensively.

Disclosed herein is thus an O-acyl product derived from glucose whichmay be obtained by partial or total esterification of vitamin F with atleast one hydroxy group of glucose.

Further disclosed herein is a composition comprising, in aphysiologically acceptable medium, at least one O-acyl product asdefined above.

Further disclosed herein is a cosmetic process for treating head hairsand/or other hairs, comprising applying to skin, the head hair and/orother hairs a cosmetic composition as defined above.

Even further disclosed herein is a cosmetic process for treating headhairs and/or other hairs, comprising applying to skin, the head hairand/or other hairs a cosmetic composition comprising an effective amountof at least one O-acyl product as defined above, leaving the compositionin contact with the head hair and/or other hairs, and optionally rinsingthe composition out.

Further disclosed herein is the use of at least one O-acyl product asdefined above for the preparation of a composition, for example, apharmaceutical composition, for improving the condition of head hairand/or other hairs, and which, for example, may be intended forachieving at least one effect chosen from reducing the loss of head hairand/or other hairs, impeding the loss of head hair and/or other hairs,inducing hair growth, and stimulating hair growth.

It is known to those skilled in the art that vitamin F, a compoundnaturally present in fatty substances and, for example, in linseed oil,sunflower oil or safflower oil, comprises a mixture of fatty acids, forexample, chosen from fatty acids comprising from C₁₂ to C₂₀hydrocarbon-based chains.

Thus, vitamin F can be considered to comprise, for example, (% byweight):

from 75% to 80% by weight of linoleic acid,

from 10% to 15% by weight of oleic acid,

from 4% to 8% by weight of palmitic acid,

from 0.5% to 3% by weight of stearic acid, and

from 0 to 10% by weight of at least one other acid chosen from lauricacid, myristic acid, arachidic acid, behenic acid, lauroleic acid,myristoleic acid, palmitoleic acid and linolenic acid.

It results therefrom that the product disclosed herein, which may beobtained by esterification of vitamin F, thus itself can comprise amixture of different esters, deriving from the presence of the variousacids, that can be formed during this reaction.

Moreover, since glucose comprises five sites capable of reacting duringthe esterification reaction, the product disclosed herein thus alsocomprises a mixture of the esters formed on the various positions ofglucose.

Finally, the product disclosed herein also comprises a mixture of themonoesters and diesters that may be formed during esterification.

As used herein, the expression “product” disclosed herein thereforemeans a mixture comprising all the monoesters and/or diesters formedduring the esterification reaction of vitamin F and glucose.

The product disclosed herein thus comprises a mixture of compounds thatmay, for example, be chosen from at least one compound of formula (I)below:

wherein:

R₁, R₂, R₃, R₄ and R₅, which may be identical or different, are eachchosen from hydrogen and radicals —CO—R wherein R is chosen fromsaturated and unsaturated, linear hydrocarbon-based chains comprisingfrom 11 to 21 carbon atoms, with the proviso that at least one of theradicals R₁ to R₅ is not hydrogen.

The ratio of the number of ester functional groups in the esterifiedproduct to the number of initial hydroxyl functional groups, or degreeof esterification, per glucose molecule may range, for example, from 0.2to 1, further, for example, from 0.2 to 0.6 and even further, forexample, from 0.21 to 0.4.

Moreover, the glucose may, for example, be esterified in at least oneposition chosen from position 1, position 2, position 3 and position 6.In one embodiment, the glucose can be esterified in at least oneposition chosen from position 1 and position 6.

The ratio of the number of ester functional groups in position 6 to thetotal number of ester functional groups, per glucose molecule, canrange, for example, from 0.55:1 to 1:1, further, for example, from0.70:1 and 0.98:1 and, even further, for example, from 0.90:1 and0.97:1.

The product disclosed herein may comprise at least one ester, forexample, at least one monoester, of glucose and of linoleic acid; atleast one ester, for example, at least one monoester, of glucose and ofoleic acid; at least one ester, for example, at least one monoester, ofglucose and of palmitic acid; and at least one ester, for example, atleast one monoester, of glucose and of stearic acid.

It may also comprise at least one ester, for example, at least onemonoester, of glucose and of at least one acid chosen from lauric acid,myristic acid, arachidic acid, behenic acid, lauroleic acid, myristoleicacid, palmitoleic acid and linolenic acid.

It may also comprise at least one diester of glucose and of at least oneacid chosen from lauric acid, myristic acid, arachidic acid, behenicacid, lauroleic acid, myristoleic acid, palmitoleic acid, linoleic acid,oleic acid, palmitic acid, stearic acid and linolenic acid.

Thus, in one embodiment, the product disclosed herein may comprise, forexample, all positions considered together:

from 40% to 80% by weight, for example, from 60% to 75% by weight andfurther, for example, from 68 to 72% by weight of at least one monoesterof glucose and of linoleic acid,

from 10% to 20% by weight, for example, from 12% to 17% by weight andfurther, for example, from 14 to 15% by weight of at least one monoesterof glucose and of oleic acid,

from 5% to 20% by weight, for example, from 7% to 15% by weight andfurther, for example, from 9 to 12% by weight of at least one monoesterof glucose and of palmitic acid,

from 0.5% to 7% by weight, for example, from 1% to 5% by weight andfurther, for example, from 2 to 4% by weight of at least one monoesterof glucose and of stearic acid,

from 0 to 10% by weight, for example, from 0.10 to 4% by weight andfurther, for example, from 0.15 to 2% by weight of at least onemonoester of glucose and of at least one acid chosen from lauric acid,myristic acid, arachidic acid, behenic acid, lauroleic acid, myristoleicacid, palmitoleic acid and linolenic acid,

0 to 10% by weight, for example, from 0.10 to 4% by weight and further,for example, from 0.15 to 2% by weight, of at least one diester ofglucose and of at least one acid chosen from lauric acid, myristic acid,arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid, linoleic acid, oleic acid, palmitic acid, stearic acidand linolenic acid.

In another embodiment, the product disclosed herein may comprise:

from 40% to 80% by weight, for example, from 60% to 75% by weight andfurther, for example, from 68 to 72% by weight of at least one ester ofglucose and of linoleic acid, for example, chosen from6-O-octadeca-9,12-dienoyl-D-glucopyranose,1-O-octadeca-9,12-dienoyl-D-glucopyranose,2-O-octadeca-9,12-dienoyl-D-glucopyranose and3-O-octadeca-9,12-dienoyl-D-glucopyranose,

from 10% to 20% by weight, for example, from 12% to 17% by weight andfurther, for example, from 14 to 15% by weight of at least one ester ofglucose and of oleic acid, for example, chosen from6-O-octadeca-9-enoyl-D-glucopyranose,3-O-octadeca-9-enoyl-D-glucopyranose,1-O-octadeca-9-enoyl-D-glucopyranose and2-O-octadeca-9-enoyl-D-glucopyranose,

from 5% to 20% by weight, for example, 7% to 15% by weight and further,for example, from 9 to 12% by weight of at least one ester of glucoseand of palmitic acid, for example, chosen from6-O-hexadecanoyl-D-glucopyranose, 3-O-hexadecanoyl-D-glucopyranose,1-O-hexadecanoyl-D-glucopyranose and 2-O-hexadecanoyl-D-glucopyranose,

from 0.5% to 7% by weight, for example, from 1% to 5% by weight andfurther, for example, from 2 to 4% by weight of at least one ester ofglucose and of stearic acid, for example, chosen from6-O-octadecanoyl-D-glucopyranose, 3-O-octadecanoyl-D-glucopyranose,1-O-octadecanoyl-D-glucopyranose and 2-O-octadecanoyl-D-glucopyranose,

from 0 to 10% by weight, for example, from 0.10 to 4% by weight, andeven further, for example, from 0.15 to 2% by weight, of at least oneester of glucose and of at least one acid chosen from lauric acid,myristic acid, arachidic acid, behenic acid, lauroleic acid, myristoleicacid, palmitoleic acid and linolenic acid,

0 to 10% by weight, for example, from 0.10 to 4% by weight, evenfurther, for example, from 0.15 to 2% by weight, of at least one diesterof glucose and of at least one acid chosen from lauric acid, myristicacid, arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid, linoleic acid, oleic acid, palmitic acid, stearic acidand linolenic acid.

The esterification reaction may, for example, be performed according toany known method. The synthesis may, for example, be performed startingwith the acid chloride (vitamin F chloride) and D-glucose, according tothe method described by Reinefeld et al. in “Die Stärke” No. 6, pages181-189, 1968.

For example, Reinefeld et al. described and compared several methods foresterifying D-glucose with lauric acid.

Among the agents for acylating glucose, it has been proposed to use acidchlorides, acid imidazolides, carboxylic-carbonic mixed anhydrides andcarboxylic anhydrides. In the case of the transesterification reactions,the agents used can be the methyl or ethyl esters of the acids.

It emerges from Reinefeld et al. that the method that can allow thehighest yield to be obtained is acylation using the acid chloride. Forexample, with lauroyl chloride, a mixture of monoester and diesters canbe obtained, in a yield of 49%, including 36% for the monoester.

This method was, for example, used in patent EP 0 485 251 to give6-O-acyl glucoses in a yield, for example, of 40% with oleyl chloride.

However, it may not always be easy to obtain the appropriate acidchloride. In the absence of industrial acid chloride, it then may benecessary to use another method.

Acylation using acid imidazolides can lead to a mixture of monoestersand diesters, in a total yield of 22% and a yield of 9% for themonoesters alone, when lauric acid imidazolide is used.

The acylation of glucose by means of forming the true anhydride can leadto the desired compounds in a total yield of 46% for the mixture ofmonoester and diesters, and of 28% for the production of the monoesters.

This process may give rise to the formation of free fatty acids that mayneed to be removed in order to lead to relatively pure end products.

However, this removal may occasionally prove to be difficult, given thenature of the impurities. Moreover, it is generally sought to avoid theintermediate purification steps, which can needlessly lengthen theprocess and can generate additional costs, this being incompatible withan industrial process.

It has been found that, irrespective of the method envisaged, theacylating agent chosen and/or the proportion of each of the reagents,the acylation of glucose could always lead to the production of amixture in which it was possible to identify D-glucopyranose 6-ester,but also D-glucopyranose 1,6-diester and D-glucopyranose 2,6-diester asco-existing reaction products.

There is thus still the need for a novel route for the synthesis ofO-acyl derivatives of glucose, which can allow the production of thesecompounds quickly and easily at the industrial level, with a large yieldof desired products.

Therefore, the present inventors sought to overcome at least one ofthese drawbacks of the prior art and to propose a process which canallow the preparation of said O-acyl derivatives of glucose in a minimumyield of about 70%.

Moreover, it has been found that the novel process disclosed herein canalso make it possible to selectively obtain glucose esters mainly inposition 6.

In addition, this process can allow the use of industrial acidchlorides.

Disclosed herein is thus a process for preparing at least one O-acylderivative mainly in position 6 of glucose, chosen from derivatives offormula (Ia):

wherein R is chosen from saturated and unsaturated, linear and branchedhydrocarbon-based chains comprising from 7 to 21 carbon atoms,comprising:

preparing a mixed anhydride of formula (II):

by reacting a carboxylic acid of formula R—COOH with a trimethylaceticacid halide of formula X—C(O)—C(CH₃)₃, wherein X may, for example, bechosen from chlorine and bromine, and

reacting said mixed anhydride formed with glucose.

The process disclosed herein can, for example, make it possible toprepare the at least one O-acyl derivative of glucose mainly in position6 chosen from derivatives of formula (Ia). The process disclosed hereinmay also make it possible, for example, to prepare the O-acyl productderived from glucose which may be obtained by partial or totalesterification of glucose and of vitamin F.

For example, the radical R can be chosen from saturated and unsaturated,linear and branched hydrocarbon-based chains comprising from 11 to 17carbon atoms.

The acyl residue —COR may, for example, be chosen from octanoyl,decanoyl, dodecanoyl, myristoyl, hexadecanoyl, stearoyl, palmitoleoyl,oleoyl, linoleoyl and linolenoyl residues.

The process disclosed herein thus comprises, in a first step, forexample, preparing a mixed anhydride of formula (II), by reacting acarboxylic acid of formula R—COOH with a trimethylacetic acid halide offormula X—C(O)—C(CH₃)₃, wherein X, for example, is chosen from chlorineand bromine.

The carboxylic acids that may be used in the process disclosed herein,may, for example, be chosen from at least one of octanoic acid, decanoicacid, dodecanoic acid, myristic acid, hexadecanoic acid, stearic acid,oleic acid, linoleic acid and linolenic acid.

The reaction scheme is then as follows:

The reaction may be performed in an organic reaction solvent, such as anorganic reaction solvent chosen from at least one of tetrahydrofuran,N,N-dimethylformamide, N-methylpyrrolidone, pyridine and toluene.

It may, for example, be performed under an inert atmosphere, forexample, under nitrogen.

At least one base may be used to activate the carboxylic acid, or thecorresponding carboxylate may be used directly; this at least one basemay, for example, be chosen from organic bases chosen, for example, fromat least one of triethylamine, pyridine, 4-dimethylaminopyridine,tributylamine and N-methylmorpholine. The reaction may be performed at atemperature ranging, for example, from −25° C. to +40° C. and further,for example, from −10° C. to +10° C., and, for example, for a durationranging from 5 minutes to 5 hours, further, for example, from 30 minutesto 3 hours.

For example, from 0.3 to 3 equivalents and further, for example, from0.5 to 1.5 equivalents of carboxylic acid can be reacted with 1equivalent of trimethylacetic acid halide.

In the esterification step of the process, said mixed anhydride can bereacted with glucose. This esterification may optionally be performedafter suction-filtering the salts possibly formed during the previousreaction.

This esterification may, for example, be performed in an organicreaction solvent, which may be the same organic reaction solvent as thatused in the preparation of the mixed anhydride of formula (II). Thisorganic reaction solvent may, for example, be chosen from at least oneof tetrahydrofuran, N,N-dimethylformamide, N-methylpyrrolidone, pyridineand toluene.

The mixed anhydride may, for example, be dissolved in said organicreaction solvent before reaction.

For example, the glucose can be dissolved beforehand in a solvent chosenfrom at least one of pyridine, dimethylformamide, N-methylpyrrolidoneand dimethylacetamide.

For example, from 0.5 to 1.5 equivalents, further, for example, from 0.9to 1.1 equivalents and even further, for example, 1 equivalent of mixedanhydride can be reacted with 3 equivalents of glucose.

At least 3 equivalents of glucose may, for example, be used relative tothe acid or the mixture of acids reacted in the previous reaction.

The esterification may be performed at a temperature ranging, forexample, from −25° C. to +100° C., further, for example, from 0° C. to+60° C. and even further, for example, from 20 to 25° C., and for aduration ranging, for example, from 1 to 30 hours, and further, forexample, from 2 to 15 hours.

After the esterification, the solvents may be separated from the desiredproduct, for example, by evaporation, centrifugation or filtration.

The resulting product may be purified by any known means, such asdistillation, chromatography on a column of silica gel, precipitationand/or extraction, for example, with a water/organic solvent mixture.

The process disclosed herein thus can make it possible in anindustrially achievable manner to prepare at least one O-acyl derivativeof glucose, mainly in position 6. For example, at least one of thefollowing O-acyl derivatives of glucose may be prepared according tothis process: 6-O-octadeca-9,12-dienoyl-D-glucopyranose;6-O-octadeca-9-enoyl-D-glucopyranose; 6-O-octadecanoyl-D-glucopyranose;and 6-O-hexadecanoyl-D-glucopyranose.

It has been found that, for example, with the process disclosed herein,glucose can mainly be esterified in position 6, and possibly in at leastone position chosen from 1, 2, and 3 positions.

The ratio of the number of ester functional groups in position 6 to thetotal number of ester functional groups per glucose molecule can range,for example, from 55% to 95%, further, for example, from 60% to 80% andeven further, for example, from 68 to 75%.

At least one O-acyl product derived from glucose disclosed herein may beused, for example, in a composition or for the preparation of acomposition that moreover comprises a physiologically acceptable medium.This composition may, for example, be in the form of a cosmeticcomposition that therefore comprises a cosmetically acceptable mediumor, for example, in the form of a pharmaceutical composition thattherefore comprises a pharmaceutically acceptable medium.

The amount of the at least one O-acyl product to be used in thecompositions disclosed herein may readily be determined by a personskilled in the art, for example, on the basis of the nature of thecomposition and/or the desired effect.

For example, this amount may range, for example, from 0.01 to 20% byweight, relative to the total weight of the composition, further, forexample, from 0.1 to 10% by weight, relative to the total weight of thecomposition, and even further, for example, from 0.5 to 5% by weight,relative to the total weight of the composition.

The physiologically, cosmetically or pharmaceutically acceptable mediumin which the product disclosed herein may be used can readily bedetermined by a person skilled in the art. It is a medium that iscompatible with application to a keratin material such as the eyelashes,the eyebrows, head hair and/or other hairs.

The medium may be anhydrous or aqueous.

The term “anhydrous medium” means a solvent medium comprising less than1% by weight of water. An anhydrous medium may comprise, for example, atleast one organic solvent chosen, for example, from C₁-C₄ alcohols, suchas ethanol; alkylene glycols, such as propylene glycol; alkylene glycoland dialkylene glycol alkyl ethers, wherein the alkyl and alkyleneradicals comprise from 1 to 4 carbon atoms.

The term “aqueous medium” means a medium comprising water or a mixtureof water and at least one other physiologically acceptable solventchosen, for example, from the at least one organic solvent mentionedabove. In the latter case, the at least one other physiologicallyacceptable solvent may, for example, be present in an amount rangingfrom 5% to 95% by weight, relative to the total weight of thecomposition.

It is possible to add to the composition, comprising the at least oneO-acyl product disclosed herein, at least one agent chosen from cosmeticand pharmaceutical active agents, for example, chosen from at least oneof:

compounds for improving the activity with respect to regrowth of thehair and/or impeding hair loss, and which have already been describedfor this activity, such as nicotinic acid esters, for example, chosenfrom tocopheryl nicotinate, benzyl nicotinate and C₁-C₆ alkylnicotinates such as methyl and hexyl nicotinate; pyrimidine derivatives,for example, 2,4-diamino-6-piperidinopyrimidine 3-oxide or “Minoxidil”described in U.S. Pat. Nos. 4,139,619 and 4,596,812; pyrimidine 3-oxidederivatives, for example, those described in documents WO 92/01437 andWO 96/09048, and, for example, “Aminexil” or 2,4-diaminopyrimidine3-N-oxide;

antibacterial agents such as macrolides, pyranosides and tetracyclins,and, for example, erythromycin;

calcium antagonists, for example, cinnarizine, diltiazem, nimodipine andnifedipine;

hormones such as oestriol and the analogues thereof, vitamin D and theanalogues thereof, and thyroxin and the salts thereof;

steroidal and non-steroidal antiinflammatory agents, such ascorticosteroids, for example, hydrocortisone;

antiandrogens, such as oxendolone, spironolactone, diethylstilbestroland flutamidem;

steroidal and non-steroidal inhibitors of 5-α-reductases, such asfinasteride and 4,6-dimethoxyindole-2-carboxylic acid and thederivatives thereof as described in European Patent No. 1 068 858;

potassium agonists such as cromakalim and nicorandil,

retinoid RXR receptor agonists and retinoid antagonists;

OH-radical scavengers such as dimethyl sulphoxide;

peptides, for example, the tripeptide Lys-Pro-Val, and for example,α-MSH and the derivatives thereof;

antidandruff and antifungal agents such as zinc pyrithione, piroctoneolamine, selenium disulphide, tropolone, hinokitiol, hinokitiol-zinc andhinokitiol-copper complexes described, for example, in European PatentNo. 0 728 478, and divalent metal complexes such as those described inFrench Patent No. 01/03309; and

free-radical scavengers; anti-seborrhoeic agents; antiparasitic agents;antiviral agents; anti-pruriginous agents.

The cosmetic and pharmaceutical active agents may also, for example, bechosen from at least one of: diazoxide, spiroxazone, phospholipids, forexample, lecithin, linoleic acid and linolenic acid; salicylic acid andthe derivatives thereof described in French Patent No. 2 581 542, forexample, salicylic acid derivatives bearing at least one alkanoyl groupcomprising from 2 to 12 carbon atoms in position 5 of the benzene ring;hydroxycarboxylic acids and keto carboxylic acids and the estersthereof; lactones and the corresponding salts thereof; anthralin,carotenoids; eicosatetraenoic acid and eicosatrienoic acid and theesters and amides thereof; and extracts of plant and bacterial origin.

At least one adjuvant commonly used in the field of application underconsideration, for example, in cosmetics, may moreover be added to thephysiologically acceptable medium, such as at least one adjuvant chosenfrom surfactants, emulsifiers, hydrophilic and lipophilic thickeners andgelling agents, cosmetic agents, preserving agents, solvents,antioxidants, UV screening agents, acidifying and basifying agents, oilsand waxes of animal, mineral, plant and synthetic origin, fillers, anddyestuffs such as pigments and colorants; these adjuvants are well knownin the prior art.

The nature and amount of the at least one adjuvant may be chosen by aperson skilled in the art on the basis of his or her general knowledge,so as to obtain the presentation form desired for the composition. Inany case, a person skilled in the art will take care to select all theoptional additional compounds and/or the amount thereof such that theadvantageous properties of the composition disclosed herein are not, orare not substantially, adversely affected by the envisaged addition(s).

The oils or waxes that may be used in the composition disclosed herein,may, for example, be chosen from at least one of mineral oils (liquidpetroleum jelly), plant oils (liquid fraction of karite butter,sunflower oil), animal oils (perhydrosqualene), synthetic oils(purcellin oil), silicone oils and waxes (cyclomethicone) and fluorooils (perfluoropolyethers), beeswax, carnauba wax and paraffin wax. Atleast one of fatty alcohols and fatty acids, such as stearic acidmay,can also be added to the oils.

The emulsifiers that can be used in the composition disclosed hereinmay, for example, be chosen from at least one of glyceryl stearate,polysorbate 60 and the mixture of PEG-6/PEG-32/glycol stearate soldunder the name Tefose 63 by the company Gattefosse.

The solvent that may be used in the composition disclosed herein may,for example, be chosen from lower alcohols, for example, ethanol andisopropanol, and propylene glycol.

The hydrophilic gelling agents that may be used in the compositiondisclosed herein may, for example, be chosen from at least one ofcarboxyvinyl polymers (carbomer), acrylic copolymers such asacrylate/alkylacrylate copolymers, polyacrylamides, polysaccharides suchas hydroxypropylcellulose, natural gums and clays. The lipophilicgelling agents that may be used in the composition disclosed herein may,for example, be chosen from at least one of modified clays, for example,bentones, metal salts of fatty acids, for example, aluminium stearatesand hydrophobic silica, ethylcellulose and polyethylene.

The compositions that may be used according to the embodiments disclosedherein may comprise other hydrophilic cosmetic and pharmaceutical activeagents, for example, chosen from at least one of proteins and proteinhydrolysates, amino acids, polyols, urea, allantoin, sugars and sugarderivatives, water-soluble vitamins, plant extracts and hydroxy acids.

The lipophilic cosmetic or pharmaceutical active agents that may be usedin the compositions disclosed herein may, for example, be chosen from atleast one of retinol (vitamin A) and the derivatives thereof, tocopherol(vitamin E) and the derivatives thereof, essential fatty acids,ceramides, essential oils, and salicylic acid and the derivativesthereof.

The compositions disclosed herein may, for example, be in anypresentation form normally used.

The compositions may, for example, be in a form chosen from aqueous andoily solutions and dispersions of lotion and serum type; emulsions ofliquid and semi-liquid consistency of the milk type, oil-in-water,water-in-oil and multiple emulsions; suspensions and emulsions of softconsistency of the aqueous and anhydrous cream and gel type;microcapsules and microparticles; vesicular dispersions of ionic and/ornonionic type. It may also be used in a form chosen from aqueous,alcoholic and aqueous-alcoholic solutions, creams, gels, emulsions andmousses, or in a form chosen from aerosol compositions furthercomprising at least one propellant under pressure.

The composition disclosed herein may, for example, be chosen fromhaircare compositions, for example, shampoos, medicated lotions andcreams, hair setting lotions, styling creams and gels; dye compositions,for example, oxidation dye compositions, optionally in the form ofcoloring shampoos; restructuring lotions for the hair; permanent-wavingcompositions (for example, compositions for the first stage of apermanent-waving operation); lotions and gels for preventing hair loss;and antiparasitic shampoos.

The compositions disclosed herein may, for example, be applied to anindividual's alopecic areas, and then may, for example, optionally beleft in contact for several hours and may, for example, optionally berinsed out.

The composition comprising an effective amount of the product disclosedherein may, for example, be applied in the evening; it may, further, forexample, be kept in contact throughout the night and a shampoo wash may,even further, for example, optionally be performed in the morning.

Further disclosed herein is a cosmetic process for treating head hairsand/or other hairs, comprising applying to skin, the head hair and/orother hairs a cosmetic composition comprising an effective amount of theproduct disclosed herein, leaving the composition in contact with thehead hair and/or other hairs, and optionally rinsing the compositionout.

The treatment process can have the characteristics of a cosmetic processin so far as it can make it possible to enhance the aesthetic appearanceof head hairs and/or other hairs, for example, by giving them greatervigour and/or improving their appearance.

The embodiments disclosed herein are illustrated in greater detail inthe examples that follow without, however, being limiting in nature.

In these examples, the compounds 6-O-octadeca-9-enoyl-D-glucopyranoseand 6-O-hexadecenoyl-D-glucopyranose were prepared according to themethod described in European Patent No. 485 251.

The compounds 6-O-octadeca-9,12-dienoyl-D-glucopyranose and6-O-octadecanoyl-D-glucopyranose were described in the literature.

EXAMPLE 1 Preparation of the Glucose Ester of Vitamin F (Mainly Ester inPosition 6)

17 ml of trimethylacetyl chloride was diluted in 100 ml oftetrahydrofuran in a 500 ml three-necked flask; a mixture of 37.3 g ofvitamin F and 19.3 ml of triethylamine predissolved in 100 ml oftetrahydrofuran was added, under an inert atmosphere and at 0° C.; themixture was stirred for 1 hour and the salts formed were then filteredoff to give a solution.

96 g of D-glucose was dissolved in 1.15 liters of pyridine in a 2 literthree-necked flask, and the above solution was added thereto, under aninert atmosphere, at room temperature. The mixture was stirredovernight.

The reaction medium was evaporated to dryness under vacuum to remove thepyridine, the paste obtained was extracted (water/organic solventmixture) and the organic phase recovered was dried, filtered andevaporated.

49 g of a yellow paste (yield: 83%) of vitamin F ester were obtained,including 72% of monoesters (mixture) in position 6.

¹H NMR spectrum (DMSO) 200 MHz: δ (ppm): 0.85; 1.23; 1.50; 2.00; 2.26;2.73; 3.03; 3.13; 3.40; 3.76; 3.97; 4.25; 4.53; 4.76; 4.89; 5.04; 5.32;6.34.

¹³C NMR spectrum (DMSO) 200 MHz: δ (ppm): 13.95; 22.12; 24.48; 25.23;26.62; 28.46 to 29.08; 31.32; 33.44; 63.91; 69.14; 70.57; 72.19; 72.86;92.30; 127.77; 129.73; 172.92.

The ¹H and ¹³C NMR spectra (DMSO) 200 MHz were in accordance with theexpected structure.

EXAMPLE 2 Preparation of the Glucose Ester of vitamin F (Mainly Ester inPosition 3)

20 g of vitamin F dissolved in 300 ml of anhydrous toluene wasintroduced into a 500 ml round-bottomed flask, under a nitrogenatmosphere, and 3 drops of DMF was added thereto to catalyze thereaction. 12.6 ml of oxalyl chloride was then added dropwise (evolutionof gas) and the mixture was stirred at 25° C. for 3 hours. The reactionmedium was concentrated to the maximum and then diluted in 200 ml ofdichloromethane. Vitamin F chloride was thus obtained, which was used inthe following step.

29.6 g of diacetone-D-glucose dissolved in 200 ml of dichloromethane,and 26 ml of triethylamine, were introduced into a 500 ml three-neckedflask on which was mounted a condenser and a dropping funnel, under anitrogen atmosphere.

The temperature was maintained at about 10° C. using an ice-water bath.

200 ml of the vitamin F chloride above was added dropwise while keepingthe temperature at about 10° C. The reaction medium was then stirred for2 hours at room temperature.

The pasty mixture obtained was diluted by adding 200 ml ofdichloromethane. The resulting mixture was then washed several times:(i) addition of distilled water and removal of the upper aqueoussolution, (ii) addition of 1N hydrochloric acid solution and removal ofthe aqueous phase, (iii) addition of distilled water and removal of theaqueous phase.

The organic phase was dried over sodium sulphate and then filtered andconcentrated to dryness.

A thick light-brown oil was obtained, which was dissolved in 350 ml of awater/trifluoroacetic acid mixture (at 11×10⁻³ mol/liter) and left atroom temperature for 1 hour. The mixture was concentrated and then takenup 5 times in 100 ml of toluene. The residue was purified on silica gel.

12 g of compound was obtained in the form of a yellow powder.

¹³C NMR (DMSO) 200 MHz: δ (ppm): 60.76; 63.82; 92.10; 92.24; 96.75;96.86

The ¹H and ¹³C NMR spectra (DMSO) 200 MHz were in accordance with theexpected structure.

EXAMPLE 3 Preparation of 3-O-octadeca-9,12-dienoyl-D-glucopyranose

29.6 g of diacetone-D-glucose dissolved in 200 ml of dichloromethane,and 26 ml of triethylamine, were introduced into a 500 ml three-neckedflask on which was mounted a condenser and a dropping funnel, under anitrogen atmosphere.

The temperature was maintained at about 10° C. using an ice-water bath.

200 ml of octadeca-9,12-dienoic(linoleic)acid chloride was addeddropwise while maintaining the temperature at about 10° C. The reactionmixture was then stirred for 2 hours at room temperature.

The pasty mixture obtained was diluted by adding 200 ml ofdichloromethane. The resulting mixture was then washed several times:(i) addition of distilled water and removal of the upper aqueoussolution, (ii) addition of 1N hydrochloric acid solution and removal ofthe aqueous phase, (iii) addition of distilled water and removal of theaqueous phase.

The organic phase was dried over sodium sulphate and then filtered andconcentrated to dryness.

21 g of a thick light-brown oil was obtained, which was dissolved in 350ml of a water/trifluoroacetic acid mixture (at 11×10⁻³ mol/liter) andleft at room temperature for 1 hour. The mixture was concentrated andthen taken up 5 times in 100 ml of toluene. The residue was purified onsilica gel.

10.8 g of compound was obtained in the form of a yellow oil (64% yield).

The ¹H and ¹³C NMR spectra (DMSO) 200 MHz were in accordance with theexpected structure.

EXAMPLE 4

It is known that one solution for impeding the propagation of theprocess that leads to the excessive loss of hair is to use cosmeticactive agents that are aimed at limiting the synthesis of mediatorsderived from the 5-lipoxygenase pathway, for example, leukotrienes.Lipoxygenase inhibitors fall within the category of these active agents.

The effect of the compounds of disclosed herein on the inhibition ofpurified soybean 15-lipoxygenase was thus tested, given that soybean15-lipoxygenase is a study model commonly used as a predictive model forhuman 5-lipoxygenase.

The test performed was as follows:

preparation of a 100 mM, pH 7.5 Tris buffer solution

preparation of a suspension of purified soybean 15-lipoxygenase L1 (0.20mg/ml) in a pH 7.5 100 mM Tris buffer; storage in ice;

calibration of the oxymeter, tank equipped with a magnetic stirringsystem and thermostatically maintained at 25° C.;

preparation of an aqueous-alcoholic solution (absolute ethanol/water,5/95, v/v) of potassium arachidonate at a concentration of 7.5 mM;

preparation of a solution of the test compound at a concentration of 30mM in dimethyl sulphoxide (DMSO);

introduction into the oxymeter tank, with stirring, of 456.6 μl ofbuffer solution, 16.7 μl of potassium arachidonate solution and 16.7 μlof solution of the test compound or 16.7 μl of DMSO in the case of the“control” measurement.

The recorder was switched on and 10 μl of suspension of 15-lipoxygenasewas introduced into the tank.

The maximum rate of consumption of oxygen (Vmax) was recorded.

The various Vmax values were compared with that of the control and theresults were expressed as a % thereof. The test was repeated 10 timesand an average of these 10 tests were determined.

The following compounds were tested:

A: 6-O-octadeca-9,12-dienoyl-D-glucopyranose

B: 6-O-octadeca-9-enoyl-D-glucopyranose

C: 6-O-octadecanoyl-D-glucopyranose

D: 6-O-hexadecanoyl-D-glucopyranose

E: 3-O-octadeca-9,12-dienoyl-D-glucopyranose

F: glucose ester of vitamin F (mainly ester in position 6)

G: glucose ester of vitamin F (mainly ester in position 3)

The following results were obtained, expressed as a % of inhibition ofthe test compound (at a concentration of 1 mM) relative to the control:

Compound % of inhibition Compound A 71% Compound B 30% Compound C 49%Compound D 15% Compound E 80% Compound F 81% Compound G 86%

It was thus found that the products disclosed herein (compounds F and G)have good capacity for inhibition of soybean lipoxygenase.

This capacity was even greater than that of the esters of glucose and ofsaturated or unsaturated C₁₈ acid, and also than that of the saturatedC₁₆ ester.

This result is particularly surprising given the fact that it would havebeen expected that this mixture of “C₁₆ esters+C₁₈ esters” (e.g.,compound F or compound G) would have been less active than the C₁₈esters alone.

EXAMPLE 5

The stability of the compounds disclosed herein were assessed (measuredby the hydrolysis of the esters).

Solutions comprising 0.1% by weight of the compounds in anethanol/isopropanol/water mixture (64/16/20 by volume) were prepared.These solutions were left in a chamber thermostatically maintained at45° C. for 2 months.

The percentage of hydrolysed glucopyranose linoleate was then determinedby HPLC.

The following results were obtained:

% of Compound hydrolysis glucose ester of vitamin F (mainly ester inposition  3% 6) 6-O-octadeca-9,12-dienoyl-D-glucopyranose  7% glucoseester of vitamin F (mainly ester in position 17% 3)3-O-octadeca-9,12-dienoyl-D-glucopyranose 30%

It was thus found that the glucose esters of vitamin F have betterstability than the glucose esters of linoleic acid.

Moreover, the stability of the ester in position 6 of glucose and ofvitamin F was slightly better than that of the same ester esterified inposition 3.

EXAMPLE 6 Daily Lotion

A composition comprising the constituents below was prepared:

compound of Example 1 0.05 g ethanol 60 g fragrance, colorants qsdemineralised water qs 100 g

EXAMPLE 7 Liposomal Gel

A composition comprising the constituents below was prepared:

compound of Example 2 0.5 g carbomer 0.25 g triethanolamine qs pH 7preserving agents qs demineralised water qs 100 g

EXAMPLE 8 Lotion for Preventing Hair Loss

A composition comprising the constituents below was prepared:

compound of Example 1 1 g propylene glycol 10 g isopropanol qs 100 g

1 ml of this lotion was applied at a rate of once or twice a day.

EXAMPLE 9 Lotion for Preventing Hair Loss

A composition comprising the constituents below was prepared:

compound of Example 2 2 g propylene glycol 30 g ethanol 40.5 g water qs100 g

This lotion was applied once or twice a day, at a rate of 1 ml perapplication.

EXAMPLE 10 Lotion for Preventing Hair Loss

A composition comprising the constituents below was prepared:

compound of Example 2 1 g propylene glycol monomethyl ether (Dowanol PMfrom 20 g Dow) hydroxypropylcellulose (Klucel G from Hercules) 3 gethanol 40 g water qs 100 g

This thickened lotion was applied once or twice a day, at a rate of oneml per application.

EXAMPLE 11 Lotion for Preventing Hair Loss

A composition comprising the constituents below was prepared:

compound of Example 1 0.2 g pyrimidine 3-oxide (Aminexil) derivative 1.5g water qs 100 g

EXAMPLE 12 Antidandruff Shampoo

A shampoo was prepared, comprising:

compound of Example 1 1.2 g salicylic acid 2 g polyglyceryl3-hydroxylauryl ether 26 g A.M. hydroxypropylcellulose (Klucel G fromHercules) 2 g preserving agent 50 g triethanolamine qs pH 7.5 water qs100 g wherein “A.M.” means active material.

This shampoo was used daily at a rate of 10 g per head of hair with anaction time of the order of 1 minute, and was applied over a period of 2weeks. A rapid drop in the sensations of pruritus and a markedimprovement in the dandruff condition were observed.

EXAMPLE 13 Antidandruff Lotion

A composition was prepared comprising:

compound of Example 2 0.3 g A.M. octopirox (piroctone olamine) 0.2 gethanol 30 g A.M. water qs 100 g wherein “A.M.” means active material.

This solution was applied daily at a rate of 6 ml, and was applied for 1to 2 weeks. A marked improvement in the dandruff condition was thenobserved.

EXAMPLE 14 Preparation of 6-O-oleoylglucose

6.02 g of trimethylacetyl chloride and 50 ml of tetrahydrofuran wereintroduced into a 250 ml three-necked flask. A mixture of 14.1 g ofoleic acid and 5.05 g of triethylamine diluted in 50 ml oftetrahydrofuran was added slowly, under an inert atmosphere and at 0° C.The mixture was stirred for 1 hour and the salts formed were thenfiltered off to obtain a solution.

36 g of glucose were dissolved in 400 ml of pyridine in a 1 literthree-necked flask, and the above solution was added thereto, under aninert atmosphere, at room temperature; stirring was continued overnight.

The reaction medium was evaporated to dryness under vacuum to remove thepyridine, the paste obtained was then extracted (water/organic solventmixture) and the recovered organic phase was dried, filtered andevaporated.

19.5 g of a white solid (87% yield) of O-oleoylglucose was obtained.

The ¹³C NMR and mass spectrum analyses were in accordance with theexpected structure.

EXAMPLE 15 Preparation of 6-O-linoleoylglucose

6.02 g of trimethylacetyl chloride and 50 ml of tetrahydrofuran wereplaced in a 250 ml three-necked flask. A mixture of 14 g of linoleicacid and 5.05 g of triethylamine diluted in 50 ml of tetrahydrofuran wasadded slowly, under an inert atmosphere and at 0° C. The mixture wasstirred for 1 hour and the salts formed were then filtered off to obtaina solution.

36 g of glucose was dissolved in 400 ml of pyridine in a 1 literthree-necked flask, and the above solution was added thereto, under aninert atmosphere, at room temperature; stirring was continued overnight.

The reaction medium was evaporated to dryness under vacuum to remove thepyridine, the paste obtained was then extracted (water/organic solventmixture) and the recovered organic phase was dried, filtered andevaporated.

18.7 g of a yellow paste (82% yield) of O-linoleoylglucose was obtained.

The yield of 6-O-linoleoylglucose was 62%.

The ¹³C NMR and mass spectrum analyses were in accordance with theexpected structure.

1. An O-acyl product prepared from a process comprising partially ortotally esterifying vitamin F with at least one hydroxy group ofglucose, wherein the vitamin F comprises: from 75% to 80% by weight oflinoleic acid, from 10% to 15% by weight of oleic acid, from 4% to 8% byweight of palmitic acid, from 0.5% to 3% by weight of stearic acid, andfrom 0 to 10% by weight of at least one additional acid chosen fromlauric acid, myristic acid, arachidic acid, behenic acid, lauroleicacid, myristoleic acid, palmitoleic acid, and linolenic acid to yieldthe O-acyl product; wherein the O-acyl product comprises, all positionsconsidered together: from 40% to 80% by weight of at least one ester ofglucose and of linoleic acid, from 10% to 20% by weight of at least oneester of glucose and of oleic acid, from 5% to 20% by weight of at leastone ester of glucose and of palmitic acid, from 0.5% to 7% by weight ofat least one ester of glucose and of stearic acid, from 0 to 10% byweight of at least one ester of glucose and of at least one acid chosenfrom lauric acid, myristic acid, arachidic acid, behenic acid, lauroleicacid, myristoleic acid, palmitoleic acid and linolenic acid, and from 0to 10% by weight of at least one diester of glucose and of at least oneacid chosen from lauric acid, myristic acid, arachidic acid, behenicacid, lauroleic acid, myristoleic acid, palmitoleic acid, linoleic acid,oleic acid, palmitic acid, stearic acid and linolenic acid; and whereinat least one of said at least one ester is a monoester.
 2. The productaccording to claim 1, further comprising at least one ester of glucoseand of at least one acid chosen from lauric acid, myristic acid,arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid and linolenic acid.
 3. The product according to claim2, wherein said at least one ester of glucose is a monoester of glucose.4. The product according to claim 1, further comprising at least onediester of glucose and of at least one acid chosen from lauric acid,myristic acid, arachidic acid, behenic acid, lauroleic acid, myristoleicacid, palmitoleic acid, linoleic acid, oleic acid, palmitic acid,stearic acid and linolenic acid.
 5. The product according to claim 1,wherein the product comprises from 60% to 75% by weight of the at leastone ester of glucose and of linoleic acid.
 6. The product according toclaim 5, wherein the product comprises from 68% to 72% by weight of theat least one ester of glucose and of linoleic acid.
 7. The productaccording to claim 1, wherein the product comprises from 12% to 17% byweight of the at least one ester of glucose and of oleic acid.
 8. Theproduct according to claim 7, wherein the product comprises from 14% to15% by weight of the at least one ester of glucose and of oleic acid. 9.The product according to claim 1, wherein the product comprises from 7%to 15% by weight of at the least one ester of glucose and of palmiticacid.
 10. The product according to claim 9, wherein the productcomprises from 9% to 12% by weight of the at least one ester of glucoseand of palmitic acid.
 11. The product according to claim 1, wherein theproduct comprises from 1% to 5% by weight of the at least one ester ofglucose and of stearic acid.
 12. The product according to claim 11,wherein the product comprises from 2% to 4% by weight of the at leastone ester of glucose and of stearic acid.
 13. The product according toclaim 1, wherein the product comprises from 0.10% to 4% by weight of theat least one ester of glucose and of at least one acid chosen fromlauric acid, myristic acid, arachidic acid, behenic acid, lauroleicacid, myristoleic acid, palmitoleic acid and linolenic acid.
 14. Theproduct according to claim 13, wherein the product comprises from 0.15%to 2% by weight of the at least one ester of glucose and of at least oneacid chosen from lauric acid, myristic acid, arachidic acid, behenicacid, lauroleic acid, myristoleic acid, palmitoleic acid and linolenicacid.
 15. The product according to claim 1, wherein the productcomprises from 0.10% to 4% by weight of the at least one diester ofglucose and of at least one acid chosen from lauric acid, myristic acid,arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid, linoleic acid, oleic acid, palmitic acid, stearic acidand linolenic acid.
 16. The product according to claim 15, wherein theproduct comprises from 0.15% to 2% by weight of the at least one diesterof glucose and of at least one acid chosen from lauric acid, myristicacid, arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid, linoleic acid, oleic acid, palmitic acid, stearic acidand linolenic acid.
 17. The product according to claim 1, wherein theglucose is esterified in at least one position chosen from position 1,position 2, position 3 and position
 6. 18. The product according toclaim 17, wherein the glucose is esterified in at least one positionchosen from position 1 and position
 6. 19. The product according toclaim 1, wherein the ratio of the number of ester functional groups inthe esterified product to the number of initial hydroxyl functionalgroups, or degree of esterification, per glucose molecule ranges from0.2 to
 1. 20. The product according to claim 19, wherein the ratio ofthe number of ester functional groups in the esterified product to thenumber of initial hydroxyl functional groups, or degree ofesterification, per glucose molecule ranges from 0.2 to 0.6.
 21. Theproduct according to claim 20, wherein the ratio of the number of esterfunctional groups in the esterified product to the number of initialhydroxyl functional groups, or degree of esterification, per glucosemolecule ranges from 0.21 to 0.4.
 22. The product according to claim 1,wherein the ratio of the number of ester functional groups in position 6to the total number of ester functional groups, per glucose molecule,ranges from 0.55:1 to 1:1.
 23. The product according to claim 22,wherein the ratio of the number of ester functional groups in position 6to the total number of ester functional groups, per glucose molecule,ranges from 0.70:1 to 0.98:1.
 24. The product according to claim 23,wherein the ratio of the number of ester functional groups in position 6to the total number of ester functional groups, per glucose molecule,ranges from 0.90:1 to 0.97:1.
 25. A composition comprising, in aphysiologically acceptable medium, at least one O-acyl product preparedfrom a process comprising partially or totally esterifying vitamin Fwith at least one hydroxy group of glucose, wherein the vitamin Fcomprises: from 75% to 80% by weight of linoleic acid, from 10% to 15%by weight of oleic acid, from 4% to 8% by weight of palmitic acid, from0.5% to 3% by weight of stearic acid, and from 0 to 10% by weight of atleast one additional acid chosen from lauric acid, myristic acid,arachidic acid, behenic acid, lauroleic acid, myristoleic acid,palmitoleic acid, and linolenic acid to yield the O-acyl product;wherein the O-acyl product comprises, all positions considered together:from 40% to 80% by weight of at least one ester of glucose and oflinoleic acid, from 10% to 20% by weight of at least one ester ofglucose and of oleic acid, from 5% to 20% by weight of at least oneester of glucose and of palmitic acid, from 0.5% to 7% by weight of atleast one ester of glucose and of stearic acid, from 0 to 10% by weightof at least one ester of glucose and of at least one acid chosen fromlauric acid, myristic acid, arachidic acid, behenic acid, lauroleicacid, myristoleic acid, palmitoleic acid and linolenic acid, and from 0to 10% by weight of at least one diester of glucose and of at least oneacid chosen from lauric acid, myristic acid, arachidic acid, behenicacid, lauroleic acid, myristoleic acid, palmitoleic acid, linoleic acid,oleic acid, palmitic acid, stearic acid and linolenic acid; and whereinat least one of said at least one ester is a monoester.
 26. Thecomposition according to claim 25, wherein the composition is in a formof a cosmetic or pharmaceutical composition comprising a cosmetically orpharmaceutically acceptable medium.
 27. The composition according toclaim 25, wherein the at least one O-acyl product is present in anamount ranging from 0.01 to 20% by weight, relative to the total weightof the composition.
 28. The composition according to claim 27, whereinthe at least one O-acyl product is present in an amount ranging from 0.1to 10% by weight, relative to the total weight of the composition. 29.The composition according to claim 28, wherein the at least one O-acylproduct is present in an amount ranging from 0.5 to 5% by weight,relative to the total weight of the composition.
 30. The compositionaccording to claim 25, wherein the physiologically acceptable medium isanhydrous or aqueous.
 31. The composition according to claim 26, whereinthe cosmetically or pharmaceutically acceptable medium is anhydrous oraqueous.
 32. The composition according to claim 25, wherein thephysiologically acceptable medium comprises at least one constituentchosen from water, organic solvents, surfactants, emulsifiers,hydrophilic and lipophilic thickeners, hydrophilic and lipophilicgelling agents, cosmetic agents, preserving agents, solvents,antioxidants, UV-screening agents, acidifying and basifying agents, oilsand waxes of animal, mineral, plant and synthetic origin, fillers,dyestuffs, and cosmetic and pharmaceutical active agents.
 33. Thecomposition according to claim 32, wherein the dyestuffs are chosen fromat least one of pigments and colorants.
 34. The composition according toclaim 32, wherein the cosmetic and pharmaceutical active agents arechosen from at least one of: compounds for improving the activity withrespect to regrowth of hair and/or impeding hair loss; antibacterialagents; calcium antagonists; hormones; steroidal and non-steroidalantiinflammatory agents; antiandrogens; steroidal and non-steroidalinhibitors of 5-α-reductases; potassium agonists; retinoid RXR receptoragonists and retinoid antagonists; OH-radical scavengers; peptides;antidandruff and antifungal agents; free-radical scavengers,anti-seborrhoeic agents, antiparasitic agents, antiviral agents,anti-pruriginous agents; diazoxide, spiroxazone, phospholipids, linoleicacid and linolenic acid, salicylic acid and the derivatives thereof;hydroxycarboxylic acids and keto carboxylic acids and the estersthereof; lactones and the corresponding salts thereof; anthralin,carotenoids; eicosatetraenoic acid and eicosatrienoic acid and theesters and amides thereof; extracts of plant and bacterial origin;proteins and protein hydrolysates, amino acids, polyols, urea,allantoin, sugars and sugar derivatives, water-soluble vitamins, plantextracts and hydroxy acids; retinol (vitamin A) and the derivativesthereof, tocopherol (vitamin E) and the derivatives thereof, essentialfatty acids, ceramides, essential oils, and salicylic acid and thederivatives thereof.
 35. The composition according to claim 34, whereinthe compounds for improving the activity with respect to regrowth ofhair and/or impeding hair loss are chosen from nicotinic acid esters.36. The composition according to claim 35, wherein the nicotinic acidesters are chosen from tocopheryl nicotinate, benzyl nicotinate andC₁-C₆ alkyl nicotinates; pyrimidine derivatives; and pyrimidine 3-oxidederivatives.
 37. The composition according to claim 36, wherein theC₁-C₆ alkyl nicotinates are chosen from methyl and hexyl nicotinates.38. The composition according to claim 36, wherein the pyrimidinederivatives are 2,4-diamino-6-piperidinopyrimidine 3-oxide.
 39. Thecomposition according to claim 36, wherein the pyrimidine 3-oxidederivatives are 2,4-diaminopyrimidine 3-N-oxide.
 40. The compositionaccording to claim 34, wherein the antibacterial agents are chosen frommacrolides, pyranosides, and tetracyclins.
 41. The composition accordingto claim 34, wherein the antibacterial agents are erythromycins.
 42. Thecomposition according to claim 34, wherein the calcium antagonists arechosen from cinnarizine, diltiazem, nimodipine, and nifedipine.
 43. Thecomposition according to claim 34, wherein the hormones are chosen fromoestriol and the analogs thereof, vitamin D and the analogs thereof, andthyroxin and the salts thereof.
 44. The composition according to claim34, wherein steroidal and non-steroidal anti-inflammatory agents arechosen from corticosteroids.
 45. The composition according to claim 44,wherein the corticosteroids are hydrocortisones.
 46. The compositionaccording to claim 34, wherein the antiandrogens are chosen fromoxendolone, spironolactone, diethylstilbestrol, and flutamide.
 47. Thecomposition according to claim 34, wherein the steroidal andnon-steroidal inhibitors of 5-α-reductases are chosen from finasterideand 4,6-dimethoxyindole-2-carboxylic acid and the derivatives thereof.48. The composition according to claim 34, wherein the potassiumagonists are chosen from cromakalim and nicorandil.
 49. The compositionaccording to claim 34, wherein the OH-radical scavengers are dimethylsulphoxides.
 50. The composition according to claim 34, wherein thepeptides are chosen from tripeptide Lys-Pro-Val and α-MSH and thederivatives thereof.
 51. The composition according to claim 34, whereinthe antidandruff and antifungal agents are chosen from zinc pyrithione,piroctone olamine, selenium disulphide, tropolone, hinokitiol,hinokitiol-zinc and hinokitiol-copper, and divalent metal complexes. 52.The composition according to claim 34, wherein the phospholids arelecithins.
 53. The composition according to claim 34, wherein thesalicylic acid and the derivatives thereof are chosen from salicylicacid derivatives thereof bearing at least one alkanoyl group comprisingfrom 2 to 12 carbon atoms in position 5 of the benzene ring.
 54. Thecomposition according to claim 25, wherein the composition is in a formchosen from aqueous and oily solutions; lotion dispersions; serumdispersions; emulsions of oil-in-water, water-in-oil and multipleemulsions; suspensions; aqueous and anhydrous gels; microcapsules andmicroparticles; ionic vesicular dispersions; nonionic vesiculardispersions; alcoholic and aqueous-alcoholic solutions; creams, gels andmousses; aerosol compositions; and solid preparations.
 55. Thecomposition according to claim 54, wherein the solid preparations arechosen from cleansing soaps and bars.
 56. The composition according toclaim 25, wherein the composition is in a form chosen from haircarecompositions, medicated lotions and creams, hair setting lotions,styling creams and gels, dye compositions, restructuring lotions forhair, permanent-waving compositions, lotions and gels for preventinghair loss, and antiparasitic shampoos.
 57. The composition according toclaim 56, wherein the haircare compositions are shampoos.
 58. Thecomposition according to claim 56, wherein the dye compositions arechosen from oxidation dye compositions optionally in the form ofcoloring shampoos.
 59. The composition according to claim 56, whereinthe permanent waving compositions are chosen from compositions for thefirst stage of a permanent-waving operation.